Quaternary methallyl ammonium halides



ii atented Feb. 27, 1940 UNITED STATES PATENT OFFICE Herman A. Bruson, Philadelphia, Pa., assignor to Riilim & Haas Company, Philadelphia,.la.

Noni-swing. Application November 10, 1936, Serial No. 110,117

7 Claims.

This invention relates to quaternary ammonium halides containing a methallyl group (CI-Iz=C(CH3)-CH2) and at least one radical containing from eight to twenty carbon atoms inclusive. The hydrocarbon chain of this large radical may be interrupted by at least one oxygen atom. This application is a continuationin-part of my copending application Serial No. 82,184, filed May 28, 1936.

It is generally known that tertiary amines will react with alkyl or aralkyl halides to form quaternary ammonium salts. The alkyl chlorides are, however, relatively inert, except at elevated temperatures and/or pressures, and for this reason it is customary to employ alkyl bromides or alkyl iodides in order to obtain satisfactory yields of the quaternary ammonium salts.

Benzyl chloride is an exception, and reacts smoothly at ordinary pressure and at room temperature, or better at 50 to 85 C., with most tertiary amines to form quaternary ammonium chlorides containing the benzyl group. These benzyl compounds are unsuited for certain purposes; for example, in insecticidal sprays they produce excessive foliage injury. Benzyl chloride is, furthermore, disagreeable to handle in the plant because of its lachrymatory and corrosive properties, and because of the difflculty in removing unreacted traces of it from the final products. The use of alkyl bromides or iodides in place of benzyl chloride is not economical because of their prohibitive cost. This situation has hampered the development of the longchained quaternary ammonium salts.

It has now been found that the methallyl halides having the formula CH2==C(CH3)CH2X, X being a halogen atom, are more reactive than the alkyl halides. The methallyl chloride reacts very easily with tertiary amines to form quaternary ammonium chlorides, particularly those containing at least one long chain at-- tached to the nitrogen atom. It has several advantages over benzyl chloride for the manufacture of quaternary ammonium salts. The cost is lower. Its boiling point is lower, therefore it can be more easily and completely removed from a reaction mixture by distillation. It is not so corrosive, hydrolyzes less readily and its odor and lachrymatory properties are considerably less ofiensive. The quaternary ammonium salts derived from it are remarkably stable, extremely soluble in water and have no harmful efiect on foliage when used as a constituent of insecticides for destroying plant pests.

Methallyl chloride reacts smoothly and rapidly with tertiary amines of the type hereinafter set forth at room temperature but it is preferably employed at 50 to 85 C. under a reflux condenser in molecularly equivalent proportions with the amine. A slight excess of the methallyl chloride is advantageously employed, and the excess subsequently removed by evaporation in vacuo or by steaming. Organic inert solvents, such as benzene, dioxane, or alcohol, can be employed if desired.

The quaternary ammonium methallyl chlorides obtained from equimolecular proportions of methallyl chloride and tertiary amines containing at least one hydrocarbon radical of eight to twenty carbon atoms which may be interrupted by one or more oxygen atoms, as set forth herein, are, in general, oily to waxy materials which dissolve in water to give foamy, soap-like solutions showing marked capillary-active properties. They can be employed as emulsifying, cleansing and dispersing agents, as wetting-out agents and dyestufi fixatives in the textile industry, and are useful as spreaders for insecti cides. They form insoluble compounds with acid dyestufis or with sulfonated organic compounds in general, and can therefore be used very advantageously in fixing these types of materials on the fibers.

This invention is illustrated by the following examples but is not limited to the exact conditions of temperature and time nor to the specific amines as it may be otherwise practiced within the scope of the appended claims.

EXAMPLE 1 Dodecyl dimethyZ-methallyl ammonium chloride A mixture of 53 parts of dodecyl dimethylamine and 23 parts of methallyl chloride is heated and stirred under a reflux condenser on a steam bath for four hours. The viscous oil obtained is heated at reduced pressure (25 mm.) at 80 to 90 in order to remove the last traces of the unreacted methallyl chloride. The product is dodecyl dimethyl-methallyl ammonium chloride having the formula o1 OH2C(CH;)=CH1 It is a pale amber-colored, viscous oil. Its 5 per cent. aqueous solution forms a heavy froth when shaken. It forms insoluble compounds with acid dyestuffs, such as Congo red, and can be used as a mordant for fixing dyes of this type on the fiber.

Exams: 2

Cetul climethyl-methallyl ammonium chloride A mixture of 67 parts 01' cetyl dimethylamine and 25 parts of methallyl chloride is heated under a reflux condenser on a steam bath for six hours. Any unreacted methallyl chloride is then removed under reduced pressure. The product,

cetyl dimethyl-methallyl ammonium chloride,

is a white, wax-like mass. Its aqueous solutions are useful as dispersing agents as, for example, in the dispersion of cuprous oxide in insecticidal compositions.

ExAurLn 3 9,10 octadeceuyl dimethyl-methallyl ammonium chloride A mixture of 28 parts of 9,10 octadecenyl' dimethylamlne, 16 parts of methallyl chloride and 25 parts of benzene is heated on a steam bath under a refiux condenser for six hours. The volatile material is then evaporated off under reduced pressure on a bath held at about 80 C. The residual 9,10 octadecenyl dimethyl-methallyl ammonium chloride having the formula is a viscous, amber-colored 011. Its aqueous solution is useful for scouring wool.

EXAMPLE 4 Secondary octyl diethyl-methallyl ammonium chloride A mixture of 18.5 parts of secondary octyl diethylamine and 10 parts of methallyl chloride is heated under a reflux condenser on a water bath for four hours. The product obtained after removal of an unreacted methallyl chloride is secondary octyl diethyl-methallyl ammonium chloride having the formula CHa(CHz)5CH(CHa)-N(C:H5)s

c1 cn'.c cm =om It is a viscous, pale yellow oil.

EXAMPLE 5 N (p a,a,'Y 'Y tetramethylbutylphenozyethoxy ethyl) -N-methallyl morpholinium chloride Its aqueous solution may be used as an emulsifying agent for oils.

Exams: 6

n-Octadecyl dimethyl-metallyl ammonium chloride A mixture of 30 parts of n-octadecyl dimethylamine, 15 parts of methallyl chloride and 50 parts of benzene is boiled for eight hours under a reflux condenser. The volatile materials are then removed by evaporation in vacuo. Theresidual n-octadecyl dimethyl-methallyl ammonium chloride having the formula is a hard, white wax. Its aqueous solution is similar in character to soap solutions.

Exams! N- (p-a,a, -tetramethulbutylphenozflethoxuethozy ethyl) -N-methallul piperidinium chloride A mixture of 40 parts of N-p-a,a,' ,'y-tetramethylbutylphenoxyethoxyethoxy ethyl piperidine (prepared from piperidine and ter-octylphenoxyethoxyethoxy ethyl chloride) and 15 parts of methallyl chloride is heated at 70 to 80 C. under reflux for seven hours and finally in vacuo at 80 C. to remove unchanged methallyl chloride. The residual product is N-(pa, 0:, 'y, 'y tetramethylbutylphenoxyethoxyethoxy ethyl) -N-methallyl piperidinium chloride having the formula It is a water-soluble, viscous oil.

The following tertiary amines may be substituted mol for mol to replace the specific amines given in the above examples to yield analogous,

water-soluble quaternary methallyl ammonium chlorides Dodecyl oxyethyl-dimethylamine CHa-(CI-Iz) 1oCH2--O-CH2-CHz-N(CH3) 2 N-octyl-N-dicyclohexylamine Gib-(CH2) a--CH:-N(Cyclohexyl) 2 N-cetyl-N-dibenzylamine GE's-(CH2) 14-CH2--N(CH2CH5) 2 p-tertiary amyl phenoxyethyl-N-dimethylamine Dodecyl diethanolamine CnH:aN(CzH4OH)2 These are given as illustrative examples of the broad class of tertiary amines which are operative for the purpose of this invention.

I claim:

1. Dodecyl dimethyl methallyl chloride.

2. A quaternary ammonium halide containing attached to the nitrogen atom a. methallyl group (CH2=C(CH3)CH2--'-) and an alkyl radical containing from eight to twenty carbon atoms, each remaining valence ofthe nitrogen atom being satisfied by a member of the group consisting of lower alkyl groups, lower alkylol groups, cycloalkyl groups, phenyl lower alkyl groups, and divalent aliphatic groups that form with the nitrogen atom a heterocyclic six-numbered, saturated ring.

3. A quaternary ammonium halide containing attached to the nitrogen atom a methallyl group (CH2=C(CH3) CI-Ia) and a radical containing from eight to twenty carbon atoms inclusive, said radical being a member of the group consisting of open chain, aliphatic hydrocarbon radicals and alkyloxy alkylene, alkylphenyl oxyalkylene, and alkylphenyl poly-oxyalkylene radicals, each remaining valence oi the nitrogen atom being satisfied by a member oi the group consisting 01' lower alh'l groups, lower alkylol ammonium groups, cycloalkyl groups, phenyl lower alkyl groups, and divalent aliphatic groups that form with the nitrogen atom a heterocyclic, six-membered, saturated ring.

4. A quaternary ammonium halide containing as its nitrogen substituents a methallyl group (CH2=C(CH3)CH2--), two lower alkyl groups and an alkyl group containing from eight. to twenty carbon atoms.

5. A quaternary ammonium halide containing as its nitrogen substituents a methaliyl group (CH2=C(CH3)CH2-), two lower alkyl groups,

and a radical containing from eight to twenty carbon atoms inclusive, said radical being a member of the group consisting of open chain, aliphatic, hydrocarbon radicals and alkyloxy alkylene, alkylphenyl oxyalkylene, and alkylv phenyl poly-oxyalkylene radicals.

6. Cetyl-dimethyl methallyl ammonium chloride.

7. n-Octadecyl dimethyl methallyl ammonium chloride.

HERMAN A. BRUSON. 

